With increasing global population comes an increase in the need to safe and clean drinking water. Contaminants can arise in drinking water either naturally, or by the interaction of disinfection chemicals with naturally occurring materials, or simply due to by-products of the disinfection mechanism itself. Due to the oxidative nature of our disinfection treatments, these species are in highly oxidized states, and in some cases require chemical reduction to become less harmful. The present work demonstrates the capabilities of aqueous phase corona plasma in reductive treatment of oxidized contaminants found in drinking water. This study focuses on the treatment of the nitrate ion, bromate ion, chlorate ion and monobromoacetic acid, all of which can be found in typical drinking water systems. The second and third chapters within this thesis establish the optimal water matrix conditions for the treatment of bromate, chlorate and nitrate. These experiments investigate the influence of pH, temperature, presence and types of oxidative scavengers, dissolved gases and by-products that are made by this treatment process with these compounds. The main conclusion of these works is that aqueous phase corona discharge is capable of producing chemical compounds with sufficient energy to chemically reduce the nitrate, bromate and chlorate anions. Acidic conditions, under low dissolved oxygen scenarios facilitated the highest amount of reduction of the target contaminants, as well as having the presence of oxidative species scavengers. It was also observed that the anoxic environment could be obtained by introducing alcohols into the contaminated solution which generated sufficient cavitation and bubbling to strip the oxygen from solution. Through a comparison of various carbonaceous compounds as oxidative species scavengers, it was determined that the volatile alcohols provided a better performance than other soluble carbon sources, due to the decrease in dissolved oxygen. The fourth chapter considers different methods of introducing argon, oxygen and nitrogen into the test solution for the effect they would have on the treatment of solutions containing the bromate anion or monobromoacetic acid. The optimal pH for the treatment of monobromoacetic acid was also established, where again the acidic conditions prevailed. Tests were conducted to consider the effect of having the solution pre-saturated with the test gas, continually sparged, or with the gas passing through a hollow discharge electrode. The tests in which gas was blown through the discharge electrode greatly surpassed all other treatment regimes, where nitrogen provided the best removal for both contaminants under acidic conditions for bromate and under acidic and basic conditions for monobromoacetic acid. The fifth chapter provides conclusions for the overall thesis and recommendations for future work. / Thesis / Doctor of Philosophy (PhD)

[EN] The main objective of this thesis is the analysis and comprehension of the association of two different combustion concepts (premixed and diffusive combustion) on the pollutant emissions and engine performance in a mid-size Diesel engine. The evaluation is performed at mid and high load conditions, where the implementation of premixed combustion is generally challenging. The association of the two combustion modes is hard to attain in a conventional Diesel engine, especially the preparation of the premixed charge with early pilot injection. Therefore, the approach followed during the study has been divided in two main steps: first, the bibliography on the subject is reviewed and two strategies avoiding the main issues mentioned in the literature are grossly evaluated in order to estimate their potential for emission reduction. Second, a deeper study of the combustion processes and emissions formation is performed, focusing only on the partially premixed combustion strategies that actually have the potential for emissions reduction. Along the second part of the study, the association of premixed and diffusive combustion is evaluated together with variation of conventional calibration parameters such as the intake oxygen concentration (via exhaust gas recirculation), the boost pressure and the start of the main injection timing, at different engine speed and load conditions. A cross analysis of the results obtained is performed in order to understand the key reasons that permit the reduction of the pollutant emissions with this strategy. In a final part of the thesis, the partially premixed combustion strategies studied are confronted with the challenges they might face when really considered for their introduction in a production engine (oil-dilution, noise...) to finally conclude on their technological potential. / [ES] El objetivo principal de la Tesis es el an álisis y la comprensi ón de la asociaci ón de dos conceptos de combusti ón diferentes (combusti ón en premezcla y por difusi ón) en las emisiones contaminantes y las prestaciones en un motor Diesel de cilindrada media. La evaluaci ón se realiza en condiciones de media y alta carga, en la cuales la implementaci ón de una combusti ón premezclada es generalmente complicada. La asociaci ón de los dos modos de combusti ón es dif cil de conseguir en un motor Diesel convencional, especialmente la preparaci ón de la carga premezclada con inyecci ón piloto adelantada. Por esa raz ón, el estudio se divide en dos partes principales: primero se revisa la bibliograf ía acerca del tema, centrando la atenci ón en dos estrategias que permiten evitar los principales problemas evocados en la literatura, determinando su potencial para la reducci ón de las emisiones contaminantes. En un segundo lugar, se realiza un estudio m as profundo de los procesos de combusti ón y de formaci ón de contaminantes, centr ándose únicamente en las estrategias de combusti ón parcialmente premezclada que sí tienen el potencial para reducir las emisiones contaminantes. En la segunda parte del estudio, se aborda la asociaci ón de combustiones premezclada y por difusi ón junto con la variaci ón de par ametros de calibraci on convencionales como la concentraci ón de ox ígeno en la admisi ón (por medio de recirculaci ón de los gases de escape), la presi ón de sobrealimentaci ón y el inicio de la inyecci ón principal, en diferentes condiciones de r egimen y de carga del motor. El an álisis cruzado de los resultados se realiza con el af án de entender las razones claves de los procesos que permiten la reducci ón de las emisiones contaminantes con esta estrategia. Como etapa final de esta tesis, se confrontan las estrategias de combusti ón parcialmente premezclada estudiadas con los problemas a los cuales podr ían llevar si realmente se considerar a su implementaci ón y un motor de serie (diluci ón de aceite, ruido...) para finalmente concluir sobre su potencial tecnol ógico. / [CA] L'objectiu principal de la tesi es l'an alisi i la comprensi o de l'associaci o de dos conceptes de combusti o diferents (combusti o en premescla i per difusi o) en les emissions contaminants i les prestacions en un motor Di esel de cilindrada mitjana. L'avaluaci o es realitza en condicions de mitja i alta c arrega, en las quals la implementaci o d'una combusti o premesclada es generalment complicada. L'associaci o dels dos modes de combusti o es dif cil d'aconseguir en un motor Di esel convencional, especialment la preparaci o de la c arrega premesclada amb injecci o pilot avan cada. Per eixa ra o, l'estudi es divideix en dos parts principals: primer es revisa la bibliogra a sobre el tema, centrant l'atenci o en dos estrat egies que permeten evitar els principals problemes evocats en la literatura, determinant el seu potencial per a la reducci o de les emissions contaminants. En un segon lloc, es realitza un estudi m es profund dels processos de combusti o i de formaci o de contaminants, centrant-se unicament en les estrat egies de combusti o parcialment premesclada que si que tenen el potencial per a reduir les emissions contaminants. En la segona part de l'estudi, s'aborda l'associaci o de combustions premesclada i per difusi o junt amb la variaci o de par ametres de calibratge convencionals com la concentraci o d'oxigen en l'admissi o (per mitj a de recirculaci o dels gasos d'escapament), la pressi o de sobrealimentaci o i l'inici de la injecci o principal, en diferents condicions de r egim i de c arrega del motor. L'an alisi creuat dels resultats es realitza amb l'afany d'entendre les raons claus dels processos que permeten la reducci o de les emissions contaminants amb esta estrat egia. Com a etapa final d'esta tesi, es confronten les estrat egies de combusti o parcialment premesclada estudiades amb els problemes als quals podrien portar si realment es consideraria la seua implementaci o en un motor de s erie (diluci o d'oli, soroll...) per a finalment concloure sobre el seu potencial tecnol ogic. / Arthozoul, SJL. (2016). Study of the association of premixed and diffusive combustion processes on the combustion and pollutant emissions in a mid-size Diesel engine [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/63262

La poudre de silicium métallurgique (MG-Si, pureté 99 %) ont été étudiées, en se focalisant particulièrement sur les particules fines (taille comprise entre 1 et 10 μm) Ce matériau est utilisé dans l’industrie siliconière pour la synthèse directe du diméthyldichlorosilane et est obtenu par broyage de blocs de silicium. Les propriétés de cette poudre sont cruciales pour le procédé industriel, à la fois en termes de surface spécifique, composition chimique et coulabilité. Comprendre l’influence des particules fines, qui dégradent la coulabilité, et leur origine au cours du broyage est donc d’une importance cruciale. Une nouvelle caractérisation, chimique et cristallographique, des poudres de MG-Si montre que les particules fines sont en moyennes moins chargées en éléments d’alliage que les particules plus grosses. La structure cristalline du silicium est inchangée au cours du broyage, sauf pour les particules superfines (taille inférieure à 1 μm). Celles-ci présentent des zones amorphes : cela montre qu’elles sont soumises à des contraintes plus importantes au cours du broyage, comme cette transformation étant obtenue au-delà d’un seuil de pression. Le comportement du MG-Si en broyage a été étudié pour la première fois. A l’échelle de la particule unique, il est confirmé que les fissures suivent une propagation transgranulaire. De plus, des particules fines peuvent être produites au cours d’un unique événement de broyage, en raison de l’activation simultanée de multiples systèmes de fissures qui peuvent brancher entre elles. La taille critique en-deçà de laquelle la déformation plastique est énergétiquement plus favorable que la propagation de fissure a été estimée à environ 1 μm par une méthode basée sur l’indentation. Ces deux résultats sont cohérents avec la répartition des éléments d’alliages en fonction de la taille de particule. A l’échelle multiparticulaire, une étude pilote en broyeur à tambour tournant a été menée. Les résultats de cette étude ne sont pas disponibles dans cette version publique du manuscrit. Veuillez vous reporter au manuscrit complet. Les conséquences sur la coulabilité de la présence de particules fines dans la poudre de MG-Si produite par broyage ont été caractérisées par mesures d’angle de repos, de dynamique de compaction et en fluidisation. En particulier, un nouveau comportement d’élutriation a été identifié et décrit : l’élutriation séquentielle se produit lorsque des particules fines sont initialement présentes dans le lit fluidisé et se caractérise par l’envolement d’abord des inférieures à environ 30 μm puis seulement des particules de taille supérieure. Ce comportement n’est pas observé en l’absence de fines dans le lit initial. L’explication de ce phénomène pourrait se trouver dans la formation de clusters polydisperses, formés seulement en présence de particules fines. En parallèle de l’élutriation séquentielle, des mesures électrostatiques avec un électromètre externe à la colonne ont montré la présence de potentiels très importants (10 kV), dont le signe correspond à la gamme de taille de particules envolées. Ceci suggère que l’adhésion au sein des clusters pourrait être électrostatique. / Metallurgical-grade silicon (MG-Si, 99 %) powders were extensively investigated, particularly focusing on the fine particles (whose size is between 1 and 10 μm) comprised in these powders. This material is a reactant widely used in the silicones industry for the Direct Synthesis and is obtained by size reduction of millimetric silicon lumps. Powder properties are major stakes of the industrial process. Smaller sizes favor high specific surfaces and high rates of production, but can decrease the lowability, thus inducing poor heat evacuation resulting in hot spots and a decrease in selectivity. Such lowability issues are particularly associated with fine particles, hence understand the generation of these particles during grinding is of critical importance. New chemical and crystallographic characterization of MG-Si is presented, showing that fine particles contain on average less alloying elements than larger particles, yet their crystallographic structure is preserved through grinding. On the contrary, superfine particles (smaller than 1 μm) exhibit amorphous zones: this transformation is pressure induced, showing that these particles experience larger stresses during the grinding step. The behavior of MG-Si in grinding mills has been studied for the first time. At the single particle level, it has been confirmed that transgranular fracture is preferred in MG-Si. Moreover, fine particles can be produced from a single fracture event, due to multiple crack propagation and branching. The critical size under which plastic deformation preferentially occurs over fracture has been evaluated to be approximately 1 μm. These two facts are consistent with a lower level of impurities in fines, yet remaining crystalline, and with superfines exhibiting amorphous areas. At the multiple particle level, pilot scale batch milling experiments have been performed. The results are not included in this public version of the manuscript, please refer to the full manuscript. The consequences of the presence of fine particles in ground MG-Si powder on lowability has been assessed by means of angle of repose, compaction tests and fluidization experiments. A new elutriation behavior has been observed and characterized: for naturally ground MS-Si powders (including fine particles), particles smaller than 30 μm are entrained first, then only larger particles. This was not the case in absence of fine particles. The explanation may probably lie within the presence of polydisperse clusters, formed only in presence of fine particles. Parallel to this elutriation behavior, electrostatic measurements with an external electrometer showed that high potential with sign correlated with the type of particle elutriated are attained during elutriation. This may suggest that electrostatics is responsible for cluster formation.

During the assembly of aircraft engines, some clearance is left in the rolling bearings mainly to reduce friction. However this clearance might allow the rolling element to vibrate during flight. Indeed, unwanted vibrations called non-synchronous vibrations (NSV) appear on the data recorded by the sensors on some development engines. NSV can be dangerous for the engine so they are closely monitored.  To prevent the appearance of the NSV, they are investigated by the engineers as soon as they appear during tests. The main source of the NSV is most likely to be the rolling bearings in the rotor because they induce a non-linear behaviour. The bearings of development engines were investigated on Finite Element Method (FEM) software for example but other methods could bring a contribution for the understanding of the NSV.  In this study, a multibody modelling software is used to try to model and explain the observed sub-synchronous vibrations considered as NSV. A model of the rotor of a prototype engine on a FEM software is provided and then reduced to be implemented in the new software. The behaviour of this new model is tested through modal analysis and response to imbalance.  Once the model is properly set, a parametric study is performed to see the effect of the thrust, gravity, imbalance weight and clearance on the system. It shows that clearance and gravity are key parameters while thrust and the imbalance weight have a minor impact on the NSV. This study has also helped to fix the parameters used to reproduce the NSV observed in the experiments.  Then, a second study focus on the influence of the clearance of the roller bearings on the NSV. This study defines a range of clearance that can be implemented on the engine to avoid the NSV. It also proved that the vibrations were very sensitive to a small change in the clearance values.  Finally, by studying the previous configurations, a link between the stiffness of the bearing and the occurrence of the NSV was established. In fact, the NSV appear only when the two roller bearings both have no stiffness because the clearance is not filled by the radial load. The rolling element is thus free to vibrate in its ring. It was noticed that the NSV has more chance to occur if it has already come out earlier in the run-up of the engine.  The multibody software is therefore perfectly able to reproduce the vibrations in a rotor. It is now a tool that can be used during the development process. / Vid montering av flygplansmotorer lämnas ett spelrum i rullningslagren främst för att minska friktionen. Detta spelrum kan emellertid tillåta att rullelementet vibrerar under flygning. Faktum är att oönskade vibrationer som kallas non-synchronous vibrations (NSV) visas på data som registreras av sensorerna på utveckling motorerna. NSV kan vara farligt för motorn och övervakas därför noggrant.För att förhindra uppkomsten av NSV utreds de regelbundet av ingenjörerna. Den huvudsakliga källan till NSV är troligen rullager i rotorn eftersom de inducerar ett icke-linjärt beteende. Lagren för utveckling motorer undersöktes till exempel med Finita Element-metoden (FEM) programvara men andra metoder skulle kunna bidra till förståelsen av NSV. I denna studie används en multibody-modelleringsprogramvara för att försöka modellera och förklara de observerade subsynkrona vibrationerna som betraktas som NSV. En modell av rotorn till en utveckling motor tillhandahålls i ett FEM-program och reduceras sedan för att implementeras i den nya mjukvaran. Beteendet hos denna nya modell testas genom modal analys och respons på obalans. När modellen är inställd utförs en parametrisk studie för att se effekten av dragkraften, gravitationen, obalansvikten och frigången i systemet.Den visar att frigång och gravitation är nyckelparametrar medan dragkraft och obalansvikt har en mindre inverkan på NSV. Denna studie har också hjälpt till att bestämma de parametrar som används för att reproducera NSV som observerats i experimenten. Därefter fokuserar en andra studie på inverkan av rullagernas frigång på NSV. Denna studie definierar ett intervall av spelrum som kan implementeras på motorn för att undvika NSV. Det visade sig också att vibrationerna var mycket känsliga för en liten ändring av frigångsvärdena.Slutligen, genom att studera de tidigare konfigurationerna, etablerades en koppling mellan lagrets styvhet och förekomsten av NSV. Faktum är att NSV endast visas när de två rullagren båda inte har någon styvhet eftersom spelet inte fylls av den radiella belastningen. Rullelementet är således fritt att vibrera i sin ring. Det märktes att NSV har större chans att inträffa om den redan sker tidigare i motorns start. Multibody-mjukvaran är därför perfekt för att reproducera vibrationerna i en rotor. Det är nu ett verktyg som kan användas under utvecklingsprocessen.

A new class of treatment processes called Advanced Reduction Processes (ARP) has been proposed. The ARPs combine activation methods and reducing agents to form highly reactive reducing radicals that degrade oxidized contaminants. Batch screening experiments were conducted to identify effective ARP by applying several combinations of activation methods (ultraviolet light, ultrasound, electron beam, microwaves) and reducing agents (dithionite, sulfite, ferrous iron, sulfide) to degradation of five target contaminants (perchlorate, nitrate, perfluorooctanoic acid, 2,4 dichlorophenol, 1,2 dichloroethane) at 3 pH levels (2.4, 7.0, 11.2). These experiments identified the combination of sulfite activated by ultraviolet light produced by a low pressure mercury vapor lamp as an effective ARP. More detailed kinetic experiments were conducted with nitrate and perchlorate as target compounds and nitrate was found to degrade more rapidly than perchlorate. The effects of pH, sulfite concentration, and light intensity on perchlorate and nitrate degradation were investigated. The effectiveness of the sulfite/UV-L treatment process improved with increasing pH for both perchlorate and nitrate.